KR20180013741A - Method of negative tone development using a copolymer multilayer electrolyte and articles made therefrom - Google Patents

Abstract

Disclosed is a multi-layered object, comprising: a substrate; and two or more layers disposed over the substrate, wherein each layer comprises a block copolymer comprising a first block and a second block. The first block comprises a repeat unit containing a hydrogen acceptor or a hydrogen donor, and the second block comprises a repeat unit containing a hydrogen donor when the repeat unit of the first block contains a hydrogen acceptor, or a hydrogen acceptor when the repeat unit of the first block contains a hydrogen donor. The first block of an innermost of the above two or more layers is bonded to the substrate, and the first block of each layer disposed over the innermost layer is bonded to the second block of a respective underlying layer. The hydrogen donor or hydrogen acceptor of the second block of an outermost the above two or more layers is blocked.

Description

TECHNICAL FIELD [0001] The present invention relates to a negative tone developing method using a copolymer multilayer electrolyte, and a method of manufacturing the negative tone developing method using the copolymer multilayer electrolyte,

The present disclosure relates to a negative tone development method using a copolymer multilayer electrolyte and an article made therefrom. In particular, the present disclosure relates to negative tone development shrink methods using block copolymer multilayer electrolytes and articles made therefrom.

In the semiconductor manufacturing industry, photoresist materials are used to transfer images to one or more base layers disposed on a semiconductor substrate, such as metal, semiconductor, and dielectric layers, as well as the substrate itself. Photoresist and photolithography process tools with high resolution capabilities have been developed and are being developed to increase the integration density of semiconductor devices and to enable the formation of structures with dimensions in the nanometer range.

Positive-Tone Chemically amplified photoresists are commonly used in high-resolution processes using positive tone development (PTD) processes. In the PTD process, the exposed area of the photoresist layer is soluble in a developing solution, typically an aqueous alkaline developer, and is removed from the substrate or substrate surface, while the unexposed areas that are insoluble in the developer remain after development, . In order to improve lithographic performance, immersion lithography tools have been developed to effectively increase the numerical aperture (NA) of imaging apparatus, for example lenses of scanners with KrF or ArF light sources. This is accomplished by the use of a relatively high refractive index fluid (i.e., immersion fluid) between the final surface of the imaging device and the upper surface of the semiconductor wafer.

Significant efforts have been made to increase the true resolution beyond what is achieved by the positive tone phenomenon from the standpoint of both materials and processes. One such example is the Negative Tone Development (NTD) process. The NTD process has an improved resolution and process window compared to a standard positive tone imaged by using superior imaging quality obtained with a bright field mask for printing a critical dark field layer. (process window). NTD resists typically utilize resins and photoacid generators having acid-labile groups (also referred to herein as acid-cleavable) groups. Exposure to actinic radiation causes the photoacid generator to form an acid which in turn causes the acid-decomposable group to separate during the post-exposure baking process, resulting in a polarity transition in the exposed area. As a result, differences in solubility characteristics occur between the exposed and unexposed areas of the resist, whereby the unexposed areas of the resist can be removed by the organic solvent developer, leaving a pattern produced by the insoluble exposed areas behind .

In order to further extend the resolution capability beyond what is typically achieved with standard resist patterning techniques, various processes for pattern shrinkage have been proposed. This process involves increasing the effective thickness of the resist pattern sidewalls to reduce (i.e. "shrink") the spacing between adjacent lines or in trench or hole patterns. In this way, trenches and contact holes formed from features, e.g., patterns, can be made smaller. Known contraction techniques include, for example, chemical vapor deposition (CVD) assist, acid diffusion resist growth and polymer blend self-assembly.

CVD assisted shrinking process (see K. Oyama et al., "The enhanced photoresist shrink process technique toward 22 nm node ", Proc . SPIE 7972, Advances in Resist Materials and Processing Technology XXVIII, 79722Q (2011) A CVD-deposited layer formed on a photoresist pattern comprising a contact hole, line / space or trench pattern. The CVD material is again etched to leave material on the sidewalls of the resist pattern. This increases the effective lateral dimension of the resist pattern, thereby reducing the open area that exposes the underlying layer to be etched. CVD assisted shrink technology requires the use of CVD and etch tools, which is costly, adds complexity to the process, and is a disadvantage in terms of process throughput.

In an acid diffusion resist growth process (also referred to as RELACS process) (see L. Peters, Resists Join Sub-λ Revolution, Semiconductor International , 1999. 9), acid- The resulting resist is coated on the patterned surface. The cross-linking of the material is catalyzed by an acid component present in the resist pattern that diffuses into the cross-linkable material during the baking step. Cross-linking occurs in the material in the vicinity of the resist pattern in the acid diffusion region and forms a coating on the sidewalls of the pattern, thereby reducing the lateral dimension of the open area of the pattern. This process typically undergoes an iso-dense bias (IDB), wherein the growth of the crosslinked layer on the resist pattern occurs non-uniformly across the die surface, depending on the density of the adjacent resist pattern (gap between). As a result, the extent of "shrinkage" for the same feature can be varied across the die based on the pattern density. This can result in patterning of defects and variations in electrical properties across the die for what is intended to be the same device.

Polymer blend self-assembly (see Y. Namie et al, "Polymer blends for directed self-assembly", Proc . SPIE 8680, Alternative Lithographic Technologies V, 86801M (2013) Lt; RTI ID = 0.0 > blend. ≪ / RTI >

The composition is then annealed, which causes the polymer to undergo phase separation, wherein the hydrophilic polymer is preferentially separated relative to the resist pattern sidewalls, and the hydrophobic polymer fills the remaining volume between the resist pattern sidewalls. The hydrophobic polymer is then removed by solvent development, leaving a hydrophilic polymer on the resist pattern sidewall. Polymer blend self-assembly has been found to experience proximity and size effects. Since the shrinkage ratio is determined by the volume ratio of the two polymers, all of the features are shrunk to the same relative percentage rather than by the same absolute amount. This can lead to the same problems described in connection with acid dispersed resist growth techniques.

There is a continuing need in the art for improved photoresist pattern shrinkage methods that address one or more problems associated with the state of the art and which enable the formation of fine patterns in electronic device fabrication.

materials; And at least two layers disposed on the substrate, wherein each layer comprises a block copolymer comprising a first block and a second block, wherein the first block comprises at least one of hydrogen Receptor or a hydrogen donor and the second block comprises a hydrogen donor if the repeat unit of the first block contains a hydrogen acceptor or a hydrogen acceptor if the repeat unit of the first block contains a hydrogen donor Containing repeating units; A first block of the innermost layer of the at least two layers is bonded to a substrate and a first block of each layer disposed on the innermost layer is bonded to a second block of each base layer; And the hydrogen donor or hydrogen acceptor of the second block of the outermost layer of the two or more layers is blocked.

Figure 1 (A) shows a photoresist substrate with no additional layers disposed thereon;
Figure 1 (B) shows the placement of the first composition on a photoresist substrate;
Figure 1 (C) shows a substrate having a first composition disposed thereon applied to an optional baking step;
1 (D) shows a second block of blocked hydrogen acceptor or blocked hydrogen donor formed on the first block;
Figure 1 (E) shows a process for the preparation of a second block comprising an unblocked hydrogen acceptor or an unblocked hydrogen donor, in the presence of an acid or acid generator, radiation and / or an agent which is deprotected by exposure to elevated temperature Two blocks;
Figure 1 (F) shows the arrangement of the first composition on the second block;
Figure 1 (G) shows the build-up of multiple layers of the block copolymer on the substrate;
Figure 2 (a) shows an upper-bottom SEM image of the line / space pattern prior to the shrink method from Example 7;
Figure 2 (b) shows an upper-lower SEM image of the line / space pattern after the shrink method from Example 8;
Fig. 2 (c) shows the top-bottom SEM image of the line / space pattern after the shrinking method from Example 9. Fig.

Shrink compositions comprising a first composition and an optional second composition are disclosed herein. The first composition comprises a block copolymer comprising at least two blocks. The two blocks include a first block and a second block wherein the first block comprises a repeating unit comprising a hydrogen acceptor or a hydrogen donor and the second block comprises a block Or a repetitive unit comprising a blocked receptor if the repeat unit of the first block is a hydrogen donor. The shrinkage composition may also comprise a solvent.

As used herein, the term "block " refers to a block polymer. Thus, the first block refers to the first block polymer and the second block refers to the second block polymer.

The second composition is the same as or different from the first composition, and comprises a block copolymer comprising a first block and a second block, wherein the first block comprises a repeating unit containing a hydrogen acceptor or a hydrogen donor, 2 block is a blocked acid when the repeating unit of the first block is a hydrogen acceptor or a repeating unit containing a blocked base when the repeating unit of the first block is a hydrogen donor; And a solvent.

Also disclosed herein is a method comprising providing a substrate and disposing a shrinkage composition on the substrate. Upon placement on the substrate, the block copolymer undergoes phase separation into two or more layers, where each layer has its largest-sized surface parallel to the substrate surface. During phase separation, the method further comprises deprotecting the hydrogen acceptor or hydrogen donor with the deprotecting agent.

Also disclosed herein is an article comprising a substrate on which a first layer and a second layer are disposed. Each layer comprises a block copolymer. The first layer comprises a first block copolymer having a first block and a second block. The first layer is the innermost layer and is reactively bonded to the substrate by covalent or ionic bonding. The first block comprises a repeating unit containing a hydrogen acceptor or a hydrogen donor and the second block comprises a blocked donor if the repeat unit of the first block is a hydrogen acceptor or a blocked donor if the repeat unit of the first block is a hydrogen donor, And a repeating unit containing a receptor.

The second layer comprises a second block copolymer comprising a first block and a second block. In the second block, the first block comprises a repeating unit containing a hydrogen acceptor or a hydrogen donor, while the second block is a blocked donor or repeating unit of the first block when the repeating unit of the first block is a hydrogen acceptor And a repeating unit containing a blocked receptor if it is a hydrogen donor. The second layer is an outermost layer and is bonded to the first layer.

In one embodiment, the first block copolymer is part of a first composition disposed on the substrate while the second block copolymer is part of a second composition disposed on the first composition after it is disposed on the substrate . In one embodiment, the first composition may be subjected to a treatment comprising removing the first composition remaining from the substrate prior to deprotecting the blocked receptor or the blocked donor of the first composition, Coating of one block copolymer is left. The arrangement of the second composition is carried out after deprotection of the blocked receptor or blocked donor of the first composition. The second composition may also be subjected to a treatment comprising removing the remaining second composition from the substrate prior to deprotecting the blocked receptor or blocked donor of the second composition, 2 < / RTI > block copolymer.

In one embodiment, the substrate is a semiconductor substrate. In another embodiment, the substrate comprises a photoresist pattern on which at least two layers are disposed, wherein the first block of the block copolymer of the innermost layer is bonded to the photoresist pattern. The photoresist pattern is formed by a negative tone development process, and the photoresist pattern includes a carboxylic acid and / or a hydroxyl group on the surface thereof.

Patterning of integrated circuits now uses smaller features than are possible with a single 193 nm wavelength exposure. A number of options exist for current hole / trench shrink features, including chemical vapor deposition (CVD) overcoating, acid diffusion resist growth and polymer blend self-assembly. CVD is undesirable due to the added complexity and cost, and acid diffusion and polymer blend methods suffer from the problems of proximity and size effects. For example, in the case of an incompatible polymer blend, since the shrinkage ratio is affected by the volume of the two components, not all features contract at the same relative percentage but at the same amount. Thus, there is a need for a spin-on solution that imparts a constant shrinkage to the pattern shrinking process regardless of feature size or density.

The first composition comprises a block copolymer. The block copolymers include diblock copolymers, triblock copolymers, star block copolymers, gradient copolymers, etc., or combinations thereof. The block copolymer comprises a first block comprising a repeating unit containing a hydrogen acceptor or a hydrogen donor and the second block comprises a blocked donor if the repeating unit of the first block is a hydrogen acceptor, Quot; is a hydrogen donor, it includes a repeating unit containing a blocked receptor. The first block and the second block are each polymer that is covalently bonded to each other. The block copolymer is sometimes referred to as a block copolymer multilayer electrolyte (BCP-ME).

In one embodiment, the block copolymer may also contain a neutral block (also referred to as an innocent block). Neutral blocks do not contain any charge species. Neutral blocks can be covalently or ionically bound to both the blocked donor block, the acceptor block, or the blocked donor block and the acceptor block in the block copolymer where the donor block is blocked. Alternatively, it can be covalently or ionically linked to both the donor block and the blocked receptor block in a copolymer comprising a donor block, a blocked receptor block or donor block and a blocked receptor block.

In one embodiment, at least one of the first block or the second block may each comprise a random copolymer of monomeric units forming a first block or a second block that is co-polymerized with the monomeric units of the neutral block.

The hydrogen acceptor containing block comprises a nitrogen-containing group. Suitable nitrogen-containing groups can form ionic bonds with acid groups on the surface of the resist pattern. Useful nitrogen-containing groups include, for example, alkylamines including amine groups and amide groups such as primary amines such as amines, secondary amines such as N-methylamine, N-ethylamine, Nt- N, N-dialkylamines including caramines such as N, N-dimethylamine, N, N-methylethylamine, N, N-diethylamine and the like. Useful amide groups include alkyl amides such as N-methyl amide, N-ethyl amide, N-phenyl amide, N, N-dimethyl amide and the like. The nitrogen-containing group may also be a ring such as pyridine, indole, imidazole, triazine, pyrrolidine, azacyclopropane, azacyclobutane, piperidine, pyrrole, purine, diazetidine, dithiazine, azokane, , Quinoline, carbazole, acridine, indazole, benzimidazole, and the like. Preferred nitrogen-containing groups are amine groups, amide groups, pyridine groups, or combinations thereof. In one embodiment, the amine in the block copolymer is attached to the block copolymer by forming an ionic bond with the free acid on the surface of the substrate (e.g., the surface of the resist to be discussed later).

In one embodiment, the repeat unit of the first block contains a hydrogen acceptor. The first block containing the hydrogen acceptor comprises a nitrogen-containing group. Examples of hydrogen acceptor-containing blocks containing a nitrogen-containing group are represented by the following formulas (1) to (2).

N is the number of repeating units, R ₁ is a C ₁ to C ₃₀ alkyl group, preferably a C ₂ to C ₁₀ alkyl group, R ₂ and R ₃ may be the same or different and are hydrogen, hydroxyl, A C ₁ to C ₃₀ alkyl group, preferably a C ₁ to C ₁₀ group, and R ₄ is hydrogen or a C ₁ to C ₃₀ alkyl group.

Wherein n, R ₁ , R _2, R ₃ and R ₄ are as defined above in the formula (1).

A preferred form of the structure of formula (2) is shown in formula (3) below:

Wherein R ₁ NR ₂ R ₃ groups are located in the para position and n, R ₁ , R _2, R ₃ and R ₄ are defined above in formula (1).

Another example of a hydrogen-containing block containing a nitrogen-containing group is shown in the following chemical formula (4).

In the formula (4), n and R ₄ are defined in formula (1), and the nitrogen atom may be in the ortho, meta, para position or any combination thereof (for example in both ortho and para positions) .

Another example of a hydrogen acceptor containing block containing a nitrogen-containing group is shown in the following chemical formula (5).

Wherein n and R < ₄ > are defined above.

Another example of a hydrogen acceptor containing block containing a nitrogen-containing group is a poly (alkyleneimine) represented by the following formula (6).

Wherein R ₁ is a 5-membered ring substituted with ₁ to 4 nitrogen atoms, R ₂ is C ₁ to C ₁₅ alkylene, and n is the total number of repeating units. An example of the structure of formula (6) is polyethyleneimine. An exemplary structure of the hydrogen acceptor of formula (6) is shown below.

As indicated above, a block comprising a hydrogen acceptor can be protected with a blocking agent if the donor group is not blocked, and vice versa. The hydrogen acceptor may be protected or blocked with an acid-decomposable group, a thermally decomposable group or a group capable of decomposing into electromagnetic radiation. In one embodiment, the acid-decomposable group can be thermally decomposed or degraded as a result of exposure to electromagnetic radiation.

An example of an acid-labile group that may be used for blocking is a C _4-30 tertiary alkyl ester. Examples of C _4-30 tertiary alkyl groups include 2- (2-methyl) propyl ("t-butyl"), 2- Cyclohexyl, 1-ethylcyclohexyl, 2-methyladamantyl, 2-ethyladamantyl, or combinations comprising at least one of the foregoing. In certain embodiments, the acid-labile group is a t-butyl group or an ethylcyclopentyl group.

Additional degradable groups for protecting the carboxylic acid include substituted methyl esters such as methoxymethyl, tetrahydropyranyl, tetrahydrofuranyl, 2- (trimethylsilyl) ethoxymethyl, benzyloxymethyl and the like; 2-substituted ethyl esters such as 2,2,2-trichloroethyl, 2-haloethyl, 2- (trimethylsilyl) ethyl and the like; 2,6-dialkylphenyl esters such as 2,6-dimethylphenyl, 2,6-diisopropylphenyl, benzyl and the like; Substituted benzyl esters such as triphenylmethyl, p-methoxybenzyl, 1-pyrenylmethyl and the like; Silyl esters such as trimethylsilyl, di-t-butylmethylsilyl, triisopropylsilyl and the like.

Examples of groups that can be cleaved by electromagnetic radiation to form free carboxylic acids or alcohols include:

Examples of groups that can be cleaved by electromagnetic radiation to form free amines include:

Additional protecting groups and methods for decomposing them are well known in the art of organic chemistry and are summarized in Greene and Wuts in "Protective groups in organic synthesis ", Third Edition, John Wiley & Sons, Inc., 1999 .

The second block (also referred to as the blocked hydrogen donor) contains a protected alcohol group and / or protected acid group when the first block contains a non-blocked hydrogen acceptor. The acid and / or alcohol groups are protected by an acid, an acid generator (e.g., a thermal acid generator or a photoacid generator), a moiety that can be deprotected by exposure to thermal energy or electromagnetic radiation. Suitable acid-decomposable groups are listed above.

The decomposition temperature of the protected group is 100 to 250 ° C. Electromagnetic radiation includes UV radiation, infrared radiation, x-rays, electron beam radiation, and the like. Exemplary protected acid groups are shown in formulas (7) to (12) below:

And wherein, n the number of the repeating units, R ₁ is C ₁ to about a C ₃₀ alkyl group, preferably C ₂ to C ₁₀ alkyl group, R ₄ is the chemical formula (7) to (12D), hydrogen, C ₁ to and C ₁₀ alkyl, R ₅ is hydrogen or C ₁ to C ₁₀ alkyl. In formula (12C), the oxygen heteroatom may be located in the ortho, meta or para position.

Other acids that may be protected may include phosphate groups and sulfonic acid groups. Blocks containing sulfonic acid groups and phosphoric acid groups that can be used in the block copolymer are shown below.

Suitable oxygen-containing groups can form hydrogen bonds with the alcohol group deprotected at the surface of the resist pattern. Useful oxygen-containing groups include, for example, ether and alcohol groups. Suitable alcohols include, for example, primary hydroxyl groups such as hydroxymethyl, hydroxyethyl, etc .; Secondary hydroxyl groups such as 1-hydroxyethyl, 1-hydroxypropyl and the like; And tertiary alcohols such as 2-hydroxypropan-2-yl, 2-hydroxy-2-methylpropyl and the like; And phenol derivatives such as 2-hydroxybenzyl, 3-hydroxybenzyl, 4-hydroxybenzyl, 2-hydroxynaphthyl and the like. Useful ether groups include, for example, methoxy, ethoxy, 2-methoxyethoxy, and the like. Other useful oxygen containing groups include diketone functional groups such as pentane-2,4-dione, and ketones such as ethanone, butanone, and the like.

Examples of protected alcohol blocks are shown in formulas (13) and (14).

Wherein n is the number of repeating units, R ₄ in formula (12) is hydrogen or C ₁ to C ₁₀ alkyl, and R ₅ is hydrogen or C ₁ to C ₁₀ alkyl.

Examples of neutral blocks are polystyrene, polyacrylate, polyolefin, polysiloxane, polycarbonate, polyacryl, polyester, polyamide, polyamideimide, polyarylate, polyarylsulfone, polyethersulfone, polyphenylene sulfide, polyvinyl A polyether ether ketone, a polyether ketone ketone, a polybenzoxazole, a polyphthalide, a polyanhydride, a polyvinyl ether, a polyvinyl thioether, a polyether sulfone, a polyether sulfone, Polyether sulfone, polyether sulfone, ether, polyvinyl ketone, polyvinyl halide, polyvinyl nitrile, polyvinyl ester, polysulfonate, polysulfide, polythioester, polysulfonamide, polyurea, polyphosphazene, polysilazane, . Exemplary neutral block polymers are shown in Formulas (15) to (17) below:

Wherein n is the number of repeating units, R ₄ is hydrogen or C ₁ to C ₁₀ alkyl, and R ₆ can be a C ₁ to C ₁₀ alkylene group;

Wherein n is the number of repeating units and R ₄ is hydrogen or C ₁ to C ₁₀ alkyl in formulas (16) and (17).

Examples of protected amine blocks (blocked or protected receptors) are shown in formulas (18) to (21) below. Examples of protected alcohols (blocked or protected receptors) are shown in formulas (22) to (24) below.

In the applicable formula (18) to (24), R ₄ is hydrogen or C ₁ to C ₁₀ alkyl, R ₇ and R ₈ are the same or different and independently represent a C ₁ to C ₃₀ alkyl group, preferably C ₁ To C < ₁₀ > groups.

Block copolymers - Examples of diblock copolymers that can be used as the multilayer electrolyte are shown below.

Diblock

Suitable block copolymers useful in the shrinkage composition include, for example, poly [(neopentyl methacrylate) -block- (N, N-dimethylaminoethyl methacrylate)], poly [neopentyl methacrylate (N, N-dimethylaminoethyl methacrylate)], poly [(tert-butylamino) ethyl methacrylate] (N, N-dimethylaminoethyl methacrylate)], poly [styrene-block- (N, N-dimethylaminoethyl methacrylate)], (2-vinylpyridine)], poly [(4-trimethylsilylstyrene) -block- (2-vinylpyridine)], poly [(trimethylsilylmethyl methacrylate) Aminoethyl methacrylate)], poly [(4-trimethylsilylstyrene) -block- (N, N-dimethylaminoethyl methacrylate)], poly [(trimethylsilylmethyl methacrylate) Poly (neopentyl methacrylate) -block- (N, N-dimethylaminoethyl methacrylate), poly (neopentyl methacrylate) -block- (N, N-dimethylaminoethyl methacrylate), poly (tert-butyl methacrylate) -block-poly (tertiary butyl methacrylate) Poly (4-trimethylsilyl) methacrylate), polystyrene-block-poly (N, N-dimethylaminoethyl methacrylate), polystyrene- Block-poly (N, N-dimethylaminoethyl methacrylate), poly (4-trimethylsilylstyrene) -block-poly (trimethylsilylmethyl methacrylate) Poly (N, N-dimethylaminoethyl methacrylate), and poly (trimethylsilylmethyl methacrylate) -block-poly (2-vinylpyridine).

Triblock copolymers with neutral blocks covalently bonded to both the hydrogen acceptor and the blocked donor block are shown below.

"Innocent" middle block and tree block

In one embodiment, the block copolymer can be a diblock or triblock copolymer, wherein each block has a pendant aromatic group. At least one block comprises a repeating unit containing a hydrogen acceptor or a hydrogen donor while the second block is a blocked donor if the repeating unit of the first block is a hydrogen acceptor or a blocked donor if the repeating unit of the first block is a hydrogen donor Lt; RTI ID = 0.0 > a < / RTI > blocked receptor. In triblock copolymers, at least one block may be a neutral block. Exemplary block copolymers in which all blocks have pendant aromatic groups are shown in formula (25) below:

Wherein n ₁ , n ₂ and n ₃ are the number of repeating units for each block and R ₈ is a C ₁ to C ₃₀ alkyl group, a hydroxyl group and the like.

By choosing a suitable block copolymer, the amount of growth of the shrink polymer on the resist pattern can be precisely controlled. Such a thickness can be adjusted, for example, by selection of a suitable molecular weight, and a high molecular weight produces a larger thickness and vice versa. The chemical composition of the shrinkage polymer can also affect the amount of growth. For example, polymers with longer unperturbed end-to-end distances or character ratios provide greater shrinkage for a given molecular weight.

The first block is present in the block copolymer in an amount of from 40 to 60 mol%, preferably from 45 to 55 mol%, based on the total number of moles of the block copolymer, while the second block is present in the block copolymer in an amount Is present in the block copolymer in an amount of from 40 to 60 mol%, preferably from 44 to 55 mol%, based on the total number of the block copolymers.

The block copolymer should have good solubility in the organic solvent used to clean and completely remove excess copolymer (i. E., Polymer not attached to the resist pattern) from the organic solvent and substrate used in the composition. The content of copolymer in the shrinkage composition will depend, for example, on the desired coating thickness of the shrinkage composition. The copolymer is typically present in the shrinkage composition in an amount of from 80 to 99 wt%, more preferably from 90 to 98 wt%, based on the total solids of the shrinkage composition. The weight average molecular weight of the polymer is typically less than 400,000, preferably from 5000 to 200,000, more preferably from 1000 to 125,000, grams (g / mol).

The first composition and the second composition may further comprise an organic solvent which may be in the form of a single organic solvent or a mixture of organic solvents. Suitable solvent materials for formulating and casting pattern processing compositions exhibit good solubility characteristics with respect to the non-solvent component of the composition, but do not significantly dissolve the underlying photoresist pattern. Suitable organic solvents for the pattern-treatment composition include, for example, alkyl esters such as n-butyl acetate, n-butyl propionate, n-pentyl propionate, n-hexyl propionate, Fionates, and alkyl butyrates such as n-butyl butyrate, isobutyl butyrate and isobutyl isobutyrate; Ketones such as 2-heptanone, 2,6-dimethyl-4-heptanone and 2,5-dimethyl-4-hexanone; Aliphatic hydrocarbons such as n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3,3-dimethylhexane and 2,3,4- Perfluoroheptane; And alcohols such as linear, branched or cyclic C ₄ -C ₉ 1 alcohols such as 1-butanol, 2-butanol, 3-methyl-1-butanol, isobutyl alcohol, tert- 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol and 4-heptanol - octanol; 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 2,2,3,3,4,4,5,5- , 3,4,4,5,5,6,6-decafluoro-1-hexanol, and C ₅ -C ₉ fluorinated diols such as 2,2,3,3,4,4-hexafluoro- 1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, and 2,2,3,3,4,4,5,5- 6,6,7,7-dodecafluoro-1,8-octanediol; Toluene, anisole, and mixtures thereof. Of these organic solvents, alkyl propionates, alkyl butyrates and ketones, preferably branched ketones, are preferred, and C ₈ -C ₉ alkyl propionate, C ₈ -C ₉ alkyl propionate, C ₈ -C ₉ Ketones, and mixtures containing at least one of these solvents. Suitable mixed solvents include, for example, alkyl ketones and alkyl propionates such as mixtures of alkyl ketones and alkyl propionates as described above. The solvent component of the composition is typically present in an amount of from 75 to 99 wt% based on the shrinkage composition.

In one method of manufacturing the photoresist, the block copolymer may be blended with a suitable amount of solvent to form the first composition. The first composition is disposed on a negative tone development (NTD) photoresist. Figure 1 shows a series of manufacturing steps of an NTD shrink substrate.

The substrate 100 may be a semiconductor such as silicon or a compound semiconductor (e.g., III-V or II-VI), glass, quartz, ceramic, Typically, the substrate is a semiconductor wafer, such as a monocrystalline silicon or compound semiconductor wafer, and may have one or more layers and patterned features formed thereon. One or more layers 102 (described in detail hereinafter) to be patterned may be provided on the substrate 100. Optionally, the base substrate material itself may be patterned, for example, if it is desired to form a trench in the substrate material. When patterning the base substrate material itself, the pattern will be considered to be formed in the layer of the substrate.

The layer can comprise, for example, one or more conductive layers such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys, nitrides or silicides of such metals, layers of doped amorphous silicon or doped polysilicon, , Silicon nitride, silicon oxynitride, or a metal oxide, a semiconductor layer such as single-crystal silicon, and combinations thereof. The layer to be etched may be formed by a variety of techniques, such as chemical vapor deposition (CVD) such as plasma-enhanced CVD, low pressure CVD or epitaxial growth, physical vapor deposition (PVD) such as sputtering or evaporation, or electroplating . The particular thickness of the one or more layers 102 to be etched will depend on the material and the particular device being formed.

A hard mask layer and / or a bottom photoresist coating (BARC) (on which a photoresist layer (not shown) is coated) is deposited on the layer 102, depending on the particular layer to be etched, the film thickness, and the photolithographic material and process used. It may be desirable to dispose such a device. The use of a hard mask layer would be desirable, for example, with a very thin resist layer, where the layer to be etched requires a significant etch depth, and / or the particular etchant has a poor resist selectivity. If a hard mask layer is used, the resist pattern to be formed will eventually be transferred to a hard mask layer that can be used as a mask to etch the base layer 102. Suitable hardmask materials and methods of formation are known in the art. Typical materials include, for example, tungsten, titanium, titanium nitride, titanium oxide, zirconium oxide, aluminum oxide, aluminum oxynitride, hafnium oxide, amorphous carbon, silicon oxynitride and silicon nitride. The hardmask layer may comprise a single layer or multiple layers of different materials. The hardmask layer may be formed by, for example, chemical or physical vapor deposition techniques.

A bottom anti-reflective coating may be desirable when reflecting a significant amount of incident radiation in a photoresist exposure process so that the substrate and / or the base layer may otherwise adversely affect the quality of the formed pattern. Such coatings can improve depth of focus, exposure latitude, line width uniformity and CD control. Antireflective coatings are typically used when the resist is exposed to deep ultraviolet light (300 nm or less), for example, KrF excimer laser light (248 nm) or ArF excimer laser light (193 nm). The antireflective coating may comprise a single layer or a plurality of different layers. Suitable antireflective materials and methods of formation are known in the art. Antireflective materials such as those sold by the ARTM brand by Dow Electronic Materials (Marlborough, Mass., USA) are commercially available, such as ARTM 40A and ARTM 124 antireflective materials.

A photoresist layer (not shown) formed from a composition such as that described herein is disposed on a substrate on an antireflective layer (if present). The photoresist composition can be applied to the substrate by spin-coating, dipping, roller-coating or other conventional coating techniques. Of these, spin coating is typical. For spin-coating, the solids content of the coating solution may be adjusted to provide the desired film thickness based on the particular coating equipment utilized, the viscosity of the solution, the rate of coating equipment and the amount of time allowed for spinning. A typical thickness for the photoresist layer is about 500 to 3000 ANGSTROM.

The photoresist layer can then be softbaked to minimize the solvent content in the layer, thereby forming a bonded dry coating and improving adhesion of the layer to the substrate. The soft bake is carried out on a hot plate or in an oven, and a hot plate is typical. The soft bake temperature and time will depend, for example, on the specific material and thickness of the photoresist. Typical soft baking is conducted at a temperature of 90 to 150 캜 and a time of about 30 to 90 seconds.

The photoresist layer is then exposed to actinic radiation through a patterned photomask (not shown) to produce a difference in solubility between the exposed and unexposed regions. Reference herein to exposure of the photoresist composition to radiation activating the composition indicates that radiation can form a latent image in the photoresist composition. The photomask has an optically transparent region and an optically opaque region, each of which corresponds to the region of the resist layer to be removed and removed in the subsequent development step. Exposure wavelengths are typically 400 nm or less, 300 nm or less, or 200 nm or less, and 248 nm, 193 nm and EUV wavelength (for example, 13.5 nm) are typical. The methods find use in immersion or dry (non-immersion) lithography techniques. The exposure energy is typically about 10 to 80 mJ / cm ² , depending on the composition of the exposure equipment and photoresist composition.

After exposure of the photoresist layer, post-exposure baking (PEB) is performed. The acid generated by the acid generator causes separation of the acid labile leaving group to form an acid group, typically a carboxylic acid group and / or an alcohol group. PEB can be carried out, for example, in a hot plate or in an oven. The conditions for PEB will depend, for example, on the specific photoresist composition and layer thickness. PEB is typically carried out at a time of about 80 to 150 DEG C, and about 30 to 90 seconds.

Figure 1 (A) shows a photoresist substrate 100 with no additional layers disposed thereon, while Figure 1 (B) shows the placement of the first composition 102 on the photoresist substrate 100 do.

The substrate 100 may be a semiconductor such as silicon or a compound semiconductor (e.g., III-V or II-VI), glass, quartz, ceramic, Typically, the substrate is a semiconductor wafer, such as a monocrystalline silicon or compound semiconductor wafer, and may have one or more layers and patterned features formed thereon. One or more layers (not shown) to be patterned may be provided on the substrate 100. Optionally, the base substrate material itself may be patterned, for example, if it is desired to form a trench in the substrate material. When patterning the base substrate material itself, the pattern will be considered to be formed in the layer of the substrate.

The layer may comprise, for example, one or more conductive layers such as aluminum, copper, molybdenum, tantalum, titanium, tungsten, alloys, nitrides or silicides of such metals, doped amorphous silicon or layers of doped polysilicon, Oxide, silicon nitride, silicon oxynitride, or a metal oxide, a semiconductor layer such as monocrystalline silicon, and combinations thereof. The layer to be etched may be formed by a variety of techniques, such as chemical vapor deposition (CVD), such as plasma-enhanced CVD, low pressure CVD or epitaxial growth, physical vapor deposition (PVD) such as sputtering or evaporation, or electroplating . The particular thickness of the one or more layers to be etched will depend on the material and the particular device being formed.

The first composition 102 may be etched using a photoresist (not shown). An optional baking step as shown in Fig. 1 (C) is then carried out on the substrate on which the first composition is disposed. Baking is carried out at a temperature above room temperature, preferably at a temperature of 70 C, or at a temperature lower than the glass transition temperature of the polymer used in the block of the block copolymer. In one embodiment, the baking may be carried out at a temperature above 110 ° C, preferably above about 130 ° C, preferably above 170 ° C. The substrate is then cleaned to remove unreacted polymer (see Fig. 1 (C)). Phase separation of the first block from the second block occurring during the batch step process and possibly the baking step promotes the development of the first block 103 containing a hydrogen acceptor or hydrogen donor on the NTD shrink substrate. A second block 104 of blocked hydrogen acceptors or blocked hydrogen donors is then formed on the first block 103 as shown in Figure 1 (D). The first block 103 and the second block 104 form a first layer. As noted above, if the first block 103 comprises a hydrogen acceptor, then the second block 104 comprises a blocked hydrogen donor. Alternatively, if the first block 103 comprises a hydrogen donor, the second block 104 comprises a blocked hydrogen donor.

After phase separation as shown in Figure 1 (E), the second block 104 is deprotected by exposure to an acid or acid generator, radiation and / or increased temperature to form an unblocked hydrogen acceptor, Forming a second block 106 comprising a blocked hydrogen donor. In one embodiment, the second block 104 is treated with an acid generator layer 105 that promotes the deprotection of the blocked hydrogen acceptor or blocked hydrogen donor to form an unblocked hydrogen acceptor or an unblocked hydrogen donor The second block 106 is formed.

The process shown in Figs. 1 (B) to 1 (E) is repeated in Figs. 1 (F) to 1 (G). In other words, different block copolymers comprising the first block and the second block, or a second composition comprising the same copolymer, are disposed on the substrate containing the first block 103 and the second block 106. The second composition is baked and cleaned as shown in Figure 1 (C) to form third and fourth blocks 107 and 108, respectively, on the photoresist substrate. The first block 107 of the second composition is similar in composition to the first block 103 formed by the deposition of the first composition and the second block 108 is formed on the photoresist substrate (Composition) similar to the second block 104 formed by the deposition of the first composition.

In another embodiment, the first block 107 and / or the second block 108 formed by deposition of the second composition comprises a first block 103 formed by deposition of a first composition on a photoresist substrate, / RTI > may be the same as or different from the first block 104 and / or the second block 104. [ In other words, the first blocks 103 and 107 may be chemically different from each other, while the second blocks 104 and 108 may be different from each other, or alternatively, the first blocks 103 and 107 may be chemically While the second blocks 104 and 108 are chemically similar to each other. As shown in Figure 1, blocks 103, 104, 107 and 108 have surfaces parallel to the surface of the photoresist base. It should be noted that blocks 103 and 104 together form the first layer while blocks 107 and 108 form the second layer.

In one embodiment, the deprotection step may be performed simultaneously on multiple layers containing a blocked hydrogen acceptor or a blocked hydrogen donor. This can be done by simultaneously treating the photoresist substrate with a plurality of first compositions and a second composition disposed thereon with an acid generator and / or electromagnetic radiation and / or thermal decomposition.

Photoresist composition

A photoresist composition useful in the present invention comprises a chemically amplified photoresist composition comprising a acid sensitive matrix resin, which is part of a layer of a photoresist composition, wherein the resin and composition layer are removed by a photo- Changes in solubility in the organic developer occur as a result of reaction with the generated acid, exposure to actinic radiation, and post-exposure baking. The change in solubility occurs when an acid-labile leaving group such as a mica-degradable ester acetal group in the matrix polymer undergoes a mine-promoted deprotection reaction upon exposure to activating radiation and heat treatment to produce an acid or alcohol group. Suitable photoresist compositions useful in the present invention are commercially available.

For imaging at a wavelength of less than a particular 200 nm, e.g., 193 nm, the matrix polymer is typically substantially free (e.g., less than 15 mole percent) or completely free of phenyl, benzyl, or other aromatic groups, The group is highly absorbing radiation. Preferred acid labile groups include, for example, tertiary acyclic alkyl carbons (e.g., t-butyl) or tertiary alicyclic carbons (e.g., methyladamantyl) that are covalently bonded to the carboxyl oxygen of the ester of the matrix polymer Containing ester group or ester group. Suitable matrix polymers further preferably include (alkyl) acrylate units comprising acid-labile (alkyl) acrylate units, such as t-butyl acrylate, t-butyl methacrylate, methyladamantyl acrylate, methyl Adamantyl methacrylate, ethylpentyl acrylate, ethylpentyl methacrylate, etc., and other non-cyclic alkyl and cycloaliphatic (alkyl) acrylates. Other suitable matrix polymers include, for example, those containing polymerized units of non-aromatic cyclic olefins (inward ring double bonds), such as optionally substituted norbornene. Two or more blends of the matrix polymers described above may suitably be used in photoresist compositions.

Suitable matrix polymers for use in photoresist compositions are commercially available and can be readily prepared by those skilled in the art. The matrix polymer is present in the resist composition in an amount sufficient to render the exposed coating layer of the resist developable in a suitable developing solution. Typically, the matrix polymer is present in the composition in an amount of 50 to 95 wt%, based on the total solids of the resist composition. The weight average molecular weight M _w of the matrix polymer is typically less than 100,000, such as 5000 to 100,000, more typically 5000 to 15,000 grams / mole.

The photoresist composition further comprises a photoacid generator (PAG) which is used in an amount sufficient to generate a latent image in the coating layer of the composition upon exposure to actinic radiation. For example, the photoacid generator will suitably be present in an amount of 1 to 20 wt%, based on the total solids of the photoresist composition. Typically, a smaller amount of PAG will be suitable for chemically amplified resists as compared to non-chemically amplified materials.

Suitable PAGs are well known in the art of chemically amplified photoresists and include, for example, the following: onium salts, such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxy Phenyl) diphenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; Nitrobenzyl derivatives such as 2-nitrobenzyl-p-toluene sulfonate, 2,6-dinitrobenzyl-p-toluene sulfonate, and 2,4-dinobenzyl-p-toluene sulfonate; Sulfonic acid esters such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, and 1,2,3-tris p-toluenesulfonyloxy) benzene; Diazomethane derivatives such as bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane; Glyoxime derivatives such as bis-O- (p-toluenesulfonyl) -? - dimethylglyoxime, and bis-O- (n-butanesulfonyl) -? - dimethylglyoxime; Sulfonic acid ester derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonic acid ester, N-hydroxysuccinimide trifluoromethanesulfonic acid ester; And halogen-containing triazine compounds such as 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- Naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine. At least one of these PAGs can be used.

Suitable solvents for photoresist compositions include, for example, glycol ethers such as 2-methoxyethyl ether (diglyme), ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; Propylene glycol monomethyl ether acetate; Lactates such as methyl lactate and ethyl lactate; Propionates such as methyl propionate, ethyl propionate, ethyl ethoxypropionate and methyl-2-hydroxyisobutyrate; Cellosolve esters such as methyl cellosolve acetate; Aromatic hydrocarbons such as toluene and xylene; And ketones such as acetone, methyl ethyl ketone, cyclohexanone and 2-heptanone. Blends of solvents such as two or more of the blends in the solvents described above are suitable. The solvent is typically present in the composition in an amount of from 90 to 99 wt%, more typically from 95 to 98 wt%, based on the total weight of the photoresist composition.

The photoresist composition may further comprise any other material. For example, the composition may include one or more of light and contrast dyes, anti-striation reagents, plasticizers, rate enhancers, sensitizers, and the like. If used, these optional additives are typically present in the composition in small amounts, e.g. 0.1 to 10 wt%, based on the total solids of the photoresist composition.

A preferred optional additive of the resist composition is an addition base. Suitable bases include, for example, linear and cyclic amides and derivatives thereof such as N, N-bis (2-hydroxyethyl) phe- bulamide, N, N-diethylacetamide, N1, N1, N3, N3-tetrabutylmalonamide, 1-methylazepan-2-one, 1-allyazepan-2-one and tert-butyl 1,3-dihydroxy- 2- (hydroxymethyl) Carbamate; Aromatic amines such as pyridine, and di-tert-butylpyridine; Aliphatic amines such as triisopropanolamine, n-tert-butyl diethanolamine, tris (2-acetoxy-ethyl) amine, 2,2 ', 2 " (Tert-butoxycarbonyl) -4-hydroxypiperidine, triethylamine, and triethylamine), tetraethanol, and 2- (dibutylamino) ethanol, 2,2 ' Butyl-2-ethyl-1H-imidazole-1-carboxylate, di-tert-butylpiperazine-1,4-dicarboxylate and N (2- Acetoxy-ethyl) morphine. The addition base is typically used in a relatively small amount, for example 0.01 to 5 wt%, preferably 0.1 to 2 wt%, based on the total solids of the photoresist composition.

The photoresist can be prepared according to a known process. For example, the resist may be prepared as a coating composition by dissolving the components of the photoresist in a suitable solvent, for example, one or more of the following: glycol ethers such as 2-methoxyethyl ether (diglyme), ethylene glycol Monomethyl ether, propylene glycol monomethyl ether; Propylene glycol monomethyl ether acetate; Lactate such as ethyl lactate or methyl lactate, ethyl lactate is preferred; Propionates, especially methyl propionate, ethyl propionate and ethyl ethoxypropionate; Cellosolve esters such as methyl cellosolve acetate; Aromatic hydrocarbons such as toluene or xylene; Or ketones such as methyl ethyl ketone, cyclohexanone and 2-heptanone. The total desired solids content of the photoresist will depend on factors such as the specific polymer in the composition, the final layer thickness, and the exposure wavelength. Typically, the solids content of the photoresist varies from 1 to 10 wt%, more typically from 2 to 5 wt%, based on the total weight of the photoresist composition.

Suitable photoresists are known in the art and include, for example, the photoresists described in U.S. Patent Nos. US20130115559A1, US20110294069A1, US20120064456A1, US20120288794A1, US20120171617A1, US20120219902A1 and US7998655B2.

The articles and methods described herein are illustrated in the following non-limiting examples.

Example

Mn and Mw, respectively, and polydispersity values, Mw / Mn or PDI, were measured on a gel permeation chromatograph on an Agilent 1100 series LC system equipped with Agilent 1100 series refractive index and MiniDAWN light scattering detector (Wyatt Technology Co.) (GPC). Samples were dissolved in HPCL grade THF at a concentration of approximately 1 mg / mL and filtered through a 0.20 μm syringe filter prior to injection via two PLGel 300 × 7.5 mm mixed C columns (5 mm, Polymer Laboratories, Inc.) . A flow rate of 1 mL / min and a temperature of 35 캜 were maintained. The column was calibrated with a narrow molecular weight PS standard (EasiCal PS-2, Polymer Laboratories, Inc.).

Proton NMR spectroscopy was performed on a Varian INOVA 400 MHz NMR spectrometer. Deuterated tetrahydrofuran was used for all NMR spectra. A delay time of 10 seconds was used to ensure complete relaxation of the protons for quantitative integration. Chemical shifts were recorded for tetramethylsilane (TMS).

All materials were commercially available and used as received unless otherwise indicated. The copolymer structures detailed in the following examples are shown below.

Example 1

This example illustrates the preparation of a first composition comprising a block copolymer containing poly (N, N'-dimethylaminoethyl methacrylate) -block-poly (t-butyl methacrylate) (PDMAEMA-b-PtBMA) Describe the synthesis.

(0.101 grams) of dimethyl 2,2'-azobis (2-methylpropionate), tert-butyl methacrylate (tBMA, 20.000 g), 2-cyanopropan-2-yl benzodithioate (CPBD, 0.389 g), ethyl acetate (20 mL) and a magnetic stir bar were charged into a 250 milliliter (mL) vial. The mixture was deoxygenated with nitrogen gas for 1 hour, after which the flask was placed in a heat block at 7O < 0 > C for 24 hours. After the reaction, the flask was cooled, ethyl acetate was kept open for 2 hours, and N ₂ was bubbled to evaporate. The reaction mixture was then dissolved in 60 mL THF and precipitated in a 1 liter (L) methanol / water mixture (9: 1). The precipitate was collected and reprecipitated. Polymer poly tert-butyl methacrylate (PtBMA) was collected and dried in a vacuum oven at room temperature overnight. Using PtBMA as the macroinitiator, 2- (dimethylamino) ethyl methacrylate (DMAEMA) monomers were polymerized using a similar procedure as described above. 3.000 g of PtBMA, 3.315 g of DMAEMA, 0.065 g of dimethyl 2,2'-azobis (2-methylpropionate) and a magnetic stir bar were charged into a 50 mL reactor. Ethyl acetate (6 mL) was deoxygenated and added to the reactor in a glovebox. The reactor was then sealed with diaphragm and placed in a heat block at 70 DEG C for 24 hours. After the reaction, the flask was cooled, ethyl acetate was kept open for 2 hours, and N ₂ was bubbled to evaporate. The reaction mixture was then dissolved in 60 mL THF and precipitated into a 1 L methanol / water mixture (9: 1). The precipitate was collected and reprecipitated. The polymer was collected and dried in a vacuum oven overnight at room temperature. The resulting PtBMA- b- PDMAEMA had Mn of 24.2 kg / mol, polydispersity index (PDI) of 1.29 and 54 mol% PDMAEMA by 1H NMR.

Example 2

This example illustrates the preparation of poly (N, N'-dimethylaminoethyl methacrylate) -block-poly (adamantyl methacrylate) -block-poly (t-butyl methacrylate) (PDMAEMA-b-PAdMA-b -PTBMA) will be described in detail. Adamanthyl methacrylate (AdMA) is a repeating unit used in the formation of a neutral block. Thus, the neutral block comprises poly (1-adamantyl methacrylate). Using PtBMA from Example 1 as a macroinitiator, AdMA monomers were polymerized using a similar procedure as described above. 2.00 g of PtBMA, 13.3 g of AdMA, 0.014 g of dimethyl 2,2'-azobis (2-methylpropionate), PGMEA (15 mL) and magnetic stir bar were charged into a 50 mL airless reactor. The mixture was frozen-pump-thawed three times, after which the flask was placed in a hot oil bath at 70 캜 for 16 hours. After the reaction, the flask was cooled and the reaction mixture was then dissolved in 10 mL THF and precipitated in 1 L acetonitrile. The precipitate was collected and reprecipitated. The polymer (PAdMA-b-PtBMA) was collected and dried in a vacuum oven at room temperature overnight. The resulting PAdMA-b-PtBMA had an Mn of 15.2 kg / mol and a PDI of 1.17.

The last block using 2- (dimethylamino) ethyl methacrylate (DMAEMA) monomer, using PAdMA-b-PtBMA as macroinitiator, was polymerized using the similar procedure described above. A mixture of 7.00 g of PAdMA-b-PtBMA, 2.10 g of DMAEMA, 0.008 g of dimethyl 2,2'-azobis (2-methylpropionate), dioxane (27 mL) Respectively. The mixture was frozen-pump-thawed three times, after which the flask was placed in a hot oil bath at 70 캜 for 16 hours. After the reaction, the flask was cooled and the reaction mixture was then dissolved in 10 mL THF and precipitated in 1 L acetonitrile. The precipitate was collected and reprecipitated. The polymer (PDMAEMA-b-PAdMA-b-PtBMA) was collected and dried in a vacuum oven at room temperature overnight. The resulting PDMAEMA-b-PAdMA-b-PtBMA had Mn of 19.5 kg / mol, PDI of 1.22 and 22.0 wt% PDMAEMA by ¹ H NMR.

Example 3

This example illustrates the preparation of poly (N, N'-dimethylaminoethyl methacrylate) -block-poly (adamantyl methacrylate-random-1,1-diphenylethyl methacrylate) (PDMAEMA- r-PPMA)). Monomer and solvent were thawed three times to remove oxygen. All three monomers were further purified prior to use with activated Al ₂ O ₃ and diluted with cyclohexane to a concentration of about 50 vol%. A required amount of tetrahydrofuran (THF) was transferred to a reactor containing pre-dried LiCl for a reaction concentration of about 7-10 wt% solids. The contents were cooled to -78 占 폚 in a dry ice / isopropanol bath. THF was titrated with sec-butyllithium (SBL) initiator in hexane at 0.7 M until green was observed. The reaction bath was warmed to room temperature until the green completely disappeared. The reaction bath was again cooled to -78 占 and 0.442 g of diphenylethylene (DPE) followed by addition of Sec butyllithium initiator (3.79 g, 0.43 M in cyclohexane) gave a bright red. ADMA (25.1 wt% solution in 38.16 g cyclohexane) and PPMA (33.5% solution in 28.5 grams cyclohexane) were added to the reaction flask and the contents stirred for 2 hours. The reaction mixture was collected by cannula insertion into the polymer mixture in anoxic methanol. The precipitated polymer was analyzed by GPC for Mn. DMAEMA monomer (1.32 g) was then added to the reaction flask and the contents stirred at -78 [deg.] C for an additional 0.5 h. The reaction aliquots were then quenched in anhydrous methanol. The reaction product was precipitated in methanol to give a white powder precipitate which was vacuum dried in an oven at 50 DEG C for 8 hours to give 20 grams of dry polymer. 1 ^st block was analyzed by GPC to obtain Mn of 43 kg / mol and Mw / Mn = 1.05.

Example 4

This embodiment details layer-by-layer growth using PDMAEMA-b-PtBMA of Example 1. [ This embodiment details the application of three layers of block copolymer on a photoresist substrate. A random copolymer (P (nBMA-r-MAA)) of n-butyl methacrylate (40%) and methacrylic acid (60%) in 4-methyl-2-pentanol (2 wt% After soft bake at < RTI ID = 0.0 > 0 C < / RTI > a film having a thickness of 62 nm was produced to produce a model anionic surface on a blank silicon wafer. The process conditions and thickness results for the steps representing sequential film growth are summarized in Table 1. 1 wt% of a block copolymer, n-butyl acetate (nBA) solution of PDMAEMA-b-PtBMA, was then applied to a film-like top coat layer for step 1 (see step 1, step A1 in FIG. , Baked at 110 [deg.] C, rinsed with nBA to remove excess material, and film thickness reported (see step 1, step A1 in Figure 1 - see Figure 1 (C)). To start step 2 (see Fig. 1 (D)), the film stack was then treated with a solution of 2 wt% isobutyl isobutyrate (IBIB) in p-toluenesulfonic acid (pTSA) (20 wt% of total solids) (NBMA-r-iBMA) (80 wt% of total solids) of butyl methacrylate (25%) and isobutyl methacrylate (75%) and the stack was then baked The nBA solution of PDMAEMA-b-PtBMA was again overcoated on the film, and the thickness of the layer was measured again (see step B1 in Figure 1) The excess material was removed and the film thickness was recorded (see Process A2 in Table 1 - see Figure 1 (G)). After the acid treatment material (Process B), the block copolymer This alternating process of (Process A) was repeated more than once to obtain three film growth layers. This process resulted in a total film growth of 16.3 nm Achieved for the further growth of the 5.7 nm in steps of 3.3 nm 1 after growth, Step 2, additional 7.3 nm after growth, and step 3.

Table 1

Example 5

This embodiment details layer growth using PDMAEMA-b-PAdMA-b-PtBMA of Example 2. [ The process conditions and thickness results for the steps representing sequential film growth are summarized in Table 2 below. This example details the application of three layers of block copolymer on a photoresist substrate.

A random copolymer (P (nBMA-r-MAA)) of n-butyl methacrylate (40%) and methacrylic acid (60%) in 4-methyl-2-pentanol (2 wt% A model anionic surface was prepared on a blank silicon wafer by producing a film having a thickness of 62.2 +/- 0.2 nm after soft-baking. For step 1, an nBA solution of 1 wt% triblock copolymer, PDMAEMA-b-PAdMA-b-PtBMA was then overcoated on the film, baked at 110 ° C and rinsed with nBA to remove excess material And the film thickness was recorded (step 1, step A1). To start step 2, the film stack was then coated with a 2 wt% IBIB solution of pTSA (20 wt% of total solids) and a random copolymer of n-butyl methacrylate (25%) and isobutyl methacrylate (75% The polymer was coated with P (nBMA-r-iBMA) (80 wt% of total solids), the stack was then baked at 150 ° C, the acid layer was rinsed with IBIB and the thickness was again measured (step B1). The nBA solution of PDMAEMA-b-PAdMA-b-PtBMA was again overcoated on the film, baked at 110 DEG C, rinsed with nBA to remove excess material, and film thickness recorded (step A2). This alternating process of the block copolymer (process A) after the material (process B) was repeated more than once to obtain three film growth layers. The process conditions and thickness results for the steps showing sequential film growth were as follows: The process is summarized in Table 1. Step 1 for total film growth at 10.7 nm Formed a 2.9 nm after growth, Step 2, additional 3.4 nm after growth, and further growth of 4.7 nm in the step 3.

Table 2

Example 6

This embodiment details layer growth using PDMAEMA-b-PAdMA-b-PtBMA of Example 2. [ The process conditions and thickness results for the steps representing sequential film growth are summarized in Table 2 below. This example details the application of four layers of block copolymer on a photoresist substrate.

A random copolymer (P (nBMA-r-MAA)) of n-butyl methacrylate (40%) and methacrylic acid (60%) in 4-methyl-2-pentanol (2 wt% ≪ RTI ID = 0.0 > 0 C < / RTI > soft-bake to produce a model NTD resist film surface on a blank silicon wafer. For step 1, an nBA solution of 1 wt% triblock copolymer, PDMAEMA-b-PAdMA-b-PtBMA was then overcoated on the film, baked at 110 ° C and rinsed with nBA to remove excess material And the film thickness was recorded (step 1, step A1). To start step 2, the film stack was then coated with a 2 wt% IBIB solution of pTSA (20 wt% of total solids) and a random copolymer of n-butyl methacrylate (25%) and isobutyl methacrylate (75% The polymer was then coated with P (nBMA-r-iBMA) (80 wt% of total solids), the stack was then baked at 130 ° C, the acid layer was cleaned by IBIB and the thickness was measured again (step B1). The nBA solution of PDMAEMA-b-PAdMA-b-PtBMA was again overcoated on the film, baked at 110 DEG C, rinsed with nBA to remove excess material, and the film thickness recorded (step A1). This alternating process of the block copolymer (process A) after the material (process B) was repeated two or more times to obtain four film growth layers. The process conditions and thickness results for the steps exhibiting sequential film growth were as follows: As in the previous example, step 1 yields 3 nm growth And the subsequent step generated greater growth. Step 2 produced additional 6.9 nm growth, step 3 produced 7.9 nm, and step 4 produced final 8.9 nm growth, resulting in a 31.9 nm Total film growth was achieved.

Table 3

Example 7

This embodiment shows the formation of a trench pattern in a negative tone developed photoresist.

A silicon wafer having a line / space pattern was first prepared and processed as follows. Inch silicon wafer with a two-layer stack of a 220 Å silicon-containing antireflective coating (SiARC) layer on a 1350 Å organic base layer. Was coated to the above-mentioned photoresist composition on a two-layer stack, TEL CLEAN TRACK ^{TM TM} LITHIUS i + coater / soft baking were aimed resist thickness of 1000Å at 90 ℃ for 60 seconds on a photoconductor.

A photoresist was prepared from the following photoresist composition. (1 wt% in methyl-2-hydroxyisobutyrate), 3.463 g PAG B solution (1 wt% in PGMEA), 6.986 g PAG E (2 wt% in methyl-2-hydroxyisobutyrate), 4.185 g trioctylamine (1 wt% solution in PGMEA), 0.248 g Polymer Additive A (25 wt% solution in PGMEA), 25.63 g PGMEA, 9.69 g Gamma-butylolactone and 22.61 g methyl-2-hydroxyisobutyrate were mixed and filtered through a 0.2 μm nylon filter.

The photoresist layer was exposed using a Dipole-35Y illumination and an ASML 1100 scanner with a numerical aperture (NA) of 0.75 through a reticle containing a line / space pattern with a pitch of 150 nm at various capacities across each wafer. Post-exposure baking was performed at 90 占 폚 for 60 seconds and the photoresist layer was developed using a n-butyl acetate (nBA) developer to form a line / space pattern with a pitch of 150 nm across the wafer and various critical dimensions (CD) . One of the resist-patterned wafers was observed by SEM as a control without further treatment, and representative SEM micrographs are shown in Fig. The average gap (CD ₁ ) between the lines was measured as 60 nm.

Example 8

This example shows the formation of shrinkage of a trench feature by application of a block copolymer. A 2-heptanone solution of 1.5 wt% of PDMAEMA-bP (AdMA-random-PPMA) and 0.15 wt% of the thermal acid generator triethylammonium para-toluenesulfonate from Example 3 was prepared, and 0.2 μm ultra high molecular weight polyethylene UPE) filter. By the two wafer from Example 7 by the spin coating of a TEL CLEAN TRACK ^TM LITHIUS ^TM i + coater / 1500 rpm on the developing device was over-coated with the solution. The patterned wafers were softbaked at 60 [deg.] C for 60 seconds and rinsed with n-butyl acetate on a spin-coater. One of the treated wafers was observed with a SEM and a typical SEM micrograph is shown in Figure _2. The average clearance (CD ₂ ) between the lines was measured at the mid-height of the pattern, CD ₂ = 46 nm, The shrinkage ΔCD _a (where ΔCD _a = CD ₁ - CD ₂ ) was calculated and ΔCD _a = 14 nm.

Example 9

This example demonstrates the formation of shrinkage of the trench feature by the application of a multilayer electrolyte type of block copolymer. A 2-heptanone solution of 1.5 wt% PDMAEMA-bP (AdMA-random-PPMA) from Example 3 was prepared and filtered through a 0.2 μm ultra high molecular weight polyethylene (UPE) filter. The wafers from Example 8 were baked at 140 DEG C for 60 seconds to induce partial deblocking of PPMA for carboxylic acid generation. The wafers were also overcoated with a block copolymer solution by spin coating at 1500 rpm on a TEL CLEAN TRACK ^TM LITHIUS ^TM i + coater / developer. The patterned wafers were softbaked at 60 [deg.] C for 60 seconds and rinsed with n-butyl acetate on a spin-coater. The resulting pattern was observed with SEM, and representative SEM micrographs are shown in Fig. 2c. The average gap (CD3) between the lines was measured on the mid-height of the pattern was CD 3 = 41 nm. Total average shrinkage [Delta] CDb (where [Delta] CDb = CD1 - CD3) is further shrinkage ΔΔCD (where ΔΔCD = ΔCD b from the second coating was of 19 nm, a block copolymer - a ΔCD) was 5 nm.

Claims (10)

A substrate; And
Wherein at least two layers disposed on the substrate
A multi-layer article comprising:
Each of said layers comprising a block copolymer comprising a first block and a second block, said first block comprising a repeating unit containing a hydrogen acceptor or a hydrogen donor, Contains a hydrogen donor when the repeating unit of the first block contains a hydrogen acceptor or a hydrogen acceptor when the repeating unit of the first block contains a hydrogen donor;
Wherein the first block of the innermost layer of the at least two layers is bonded to the substrate and the first block of each layer disposed on the innermost layer is bonded to a second block of each base layer; Wherein the hydrogen donor or hydrogen acceptor of the second block of the outermost layer of the at least two layers is blocked. The method of claim 1, wherein the at least two layers comprise a first layer and a second layer, wherein the first layer is the innermost layer and is bonded to the substrate, the second layer is the outermost layer, Wherein the first layer is bonded to the first layer. The multi-layer article of claim 1 or 2, wherein the repeating unit of the first block contains a hydrogen acceptor. 4. The article of claim 3, wherein the repeating unit of the first block containing the hydrogen acceptor comprises a nitrogen-containing group. 5. The multi-layer article of claim 4, wherein the nitrogen-containing group is selected from an amine group, an amide group and a pyridine group. 3. The multi-layer article of claim 1 or 2, wherein the repeating unit of the first block contains a hydrogen donor. 3. The multi-layer article of claim 1 or 2, wherein at least one of the block copolymers further comprises a block of neutral polymer disposed between the first block and the second block. 8. The multilayer article according to any one of claims 1 to 7, wherein the substrate is a semiconductor substrate. 9. The multilayer article of claim 8, wherein the substrate comprises a photoresist pattern over which at least two layers are disposed, wherein the first block of the block copolymer of the innermost layer is bonded to the photoresist pattern. The multi-layer article of claim 9, wherein the photoresist pattern is formed by a negative tone development process, the photoresist pattern comprising a carboxylic acid group and / or a hydroxyl group on the surface.

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